Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 6

February 4, 2013

Volume 52, Issue 6

Pages 1597–1838

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. You have free access to this content
      Cover Picture: Synthesis and Structure of Tetraarylcumulenes: Characterization of Bond-Length Alternation versus Molecule Length (Angew. Chem. Int. Ed. 6/2013) (page 1597)

      Johanna A. Januszewski, Dominik Wendinger, Christian D. Methfessel, Dr. Frank Hampel and Prof. Rik R. Tykwinski

      Article first published online: 29 JAN 2013 | DOI: 10.1002/anie.201210205

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      sp-Hybridized carbon allotropes based on a polyyne framework are well documented, while properties of the cumulenic form of these allotropes remain mysterious. In their Communication on page 1817 ff., R. R. Tykwinski and co-workers shed new light on the properties of cumulenes (such as bond length alternation) through the synthesis, spectroscopic study, and crystallographic analysis of cumulenes that contain up to nine consecutive double bonds (i.e., a [9]cumulene). Cover art: Annie Tykwinski; based on a concept from D. Wendinger.

    2. You have free access to this content
      Inside Cover: Mechanism of Carbon Dioxide Adsorption in a Highly Selective Coordination Network Supported by Direct Structural Evidence (Angew. Chem. Int. Ed. 6/2013) (page 1598)

      Anna M. Plonka, Dr. Debasis Banerjee, William R. Woerner, Zhijuan Zhang, Nour Nijem, Prof. Dr. Yves J. Chabal, Prof. Dr. Jing Li and Prof. Dr. John B. Parise

      Article first published online: 16 JAN 2013 | DOI: 10.1002/anie.201210206

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      Understanding of gas adsorption mechanisms at the molecular level is vital for the rational development of compounds that can remove harmful greenhouse gases from the atmosphere. In their Communication on page 1692 ff., J. Li and J. B. Parise et al. describe the adsorption of CO2 molecules in a “pocket” between two aromatic rings of a nanoporous coordination network. The CO2–framework interaction is characterized by a combination of methods.

    3. You have free access to this content
      Inside Back Cover: The Fold-In Approach to Bowl-Shaped Aromatic Compounds: Synthesis of Chrysaoroles (Angew. Chem. Int. Ed. 6/2013) (page 1839)

      Damian Myśliwiec and Dr. Marcin Stępień

      Article first published online: 16 JAN 2013 | DOI: 10.1002/anie.201210137

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      The synthesis of chrysaorole , which is a jellyfish-shaped heteroaromatic molecule, is described by D. Myśliwiec and M. Stępień in their Communication on page 1713 ff. This strained system was obtained from a carbazole-based macrocyclic precursor by using a new “fold-in” strategy.

    4. You have free access to this content
      Back Cover: Conversion of a Singlet Silylene to a stable Biradical (Angew. Chem. Int. Ed. 6/2013) (page 1840)

      Dr. Kartik Chandra Mondal, Prof. Dr. Herbert W. Roesky, Martin C. Schwarzer, Prof. Dr. Gernot Frenking, Dr. Igor Tkach, Hilke Wolf, Daniel Kratzert, Dr. Regine Herbst-Irmer, Benedikt Niepötter and Prof. Dr. Dietmar Stalke

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201210325

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      Colored stable biradicals are described by H. W. Roesky, G. Frenking, I. Tkach, D. Stalke, and co-workers in their Communication on page 1801 ff.; they were prepared from SiCl2, which is stabilized by an N-heterocyclic carbene, and a cyclic alkyl(amino)carbene. The deep-blue crystals of one polymorph of the product are stable upon exposure to air for about a week, while the solution in THF decomposes rapidly when exposed to air. A C[BOND]C bond formation can be observed in a side reaction of the synthesis.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 6/2013 (pages 1601–1614)

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201390003

  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
  4. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Mathias Christmann (page 1624)

      Article first published online: 20 SEP 2012 | DOI: 10.1002/anie.201207021

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      “Chemistry is fun because it creates its own object (Berthelot). My favorite way to spend a holiday is with a rental car, lots of time, and no itinerary …” This and more about Mathias Christmann can be found on page 1624.

  5. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
  6. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Applied Homogeneous Catalysis. By Arno Behr and Peter Neubert. (page 1627)

      Paul S. Pregosin

      Article first published online: 19 DEC 2012 | DOI: 10.1002/anie.201208808

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      Wiley-VCH, Weinheim, 2012. 688 pp., softcover, € 69.00.—ISBN 978-3527326334

  7. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Biosensing

      Lighting up Carbon Monoxide: Fluorescent Probes for Monitoring CO in Living Cells (pages 1628–1630)

      Lin Yuan, Prof. Weiying Lin, Li Tan, Kaibo Zheng and Weimin Huang

      Article first published online: 13 DEC 2012 | DOI: 10.1002/anie.201208346

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      All aglow: Both a fluorescent biosensor, composed of a circularly permuted yellow fluorescent protein (cpYFP), and a small-molecule fluorescent probe (1) for the detection of CO in living cells have been recently reported. Though different these novel probes were designed based on the unique binding ability of CO to transition-metal ions.

    2. Magnetic Properties

      Skyrmions (pages 1631–1634)

      Prof. Claudia Felser

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201207056

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      Topologically stable magnetic screw-like nanostructures called skyrmions were designed by using the concept of topology and the guidance of theory. These particles in real space are found in non-centrosymmetric compounds such as MnSi. Skyrmions might have an enormous impact in the context of future spintronics applications.

  8. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Antibacterial Silver

      Silver as Antibacterial Agent: Ion, Nanoparticle, and Metal (pages 1636–1653)

      Svitlana Chernousova and Prof. Dr. Matthias Epple

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201205923

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      Silver shield: Silver is used in different forms as an antibacterial agent. Earlier, sparingly soluble silver salts were predominantly used, but today, silver nanoparticles (see picture for an SEM image of cubic silver nanoparticles) are gaining increasing importance. As silver is also toxic towards mammalian cells, there is the question of the therapeutic window in the cases of consumer products and medical devices.

  9. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Review
    10. Communications
    1. Conducting Materials

      Stretchable Conductors Based on Silver Nanowires: Improved Performance through a Binary Network Design (pages 1654–1659)

      Jin Ge, Dr. Hong-Bin Yao, Xu Wang, Yin-Dong Ye, Jin-Long Wang, Zhen-Yu Wu, Dr. Jian-Wei Liu, Feng-Jia Fan, Huai-Ling Gao, Chuan-Lin Zhang and Prof. Dr. Shu-Hong Yu

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201209596

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      Stretching the role of a conductor: A new kind of polyurethane sponge–Ag nanowire–poly(dimethylsiloxane) (PUS-AgNW-PDMS) stretchable conductors can be easily fabricated based on a novel binary network structure design, which greatly enhances their electronic performance. These PUS-AgNW-PDMS elastomeric conductors show improved electromechanical stability compared to previously reported stretchable conductors.

    2. Gold Complexes

      Generation and Structural Characterization of a Gold(III) Alkene Complex (pages 1660–1663)

      Eirin Langseth, Margaret L. Scheuermann, Dr. David Balcells, Prof. Werner Kaminsky, Prof. Karen I. Goldberg, Prof. Odile Eisenstein, Dr. Richard H. Heyn and Prof. Mats Tilset

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201209140

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      A Missing Gold Link: An AuIII alkene complex has been prepared and characterized by NMR spectroscopy and X-ray crystallography. Its bonding features have been analyzed by DFT calculations and natural bond orbital (NBO) analysis. In [(cod)AuMe2]+, the unequal Au[BOND]C bond lengths result from the domination of the preference of 1,5-cyclooctadiene (cod) for nonparallel double bonds over back donation from the metal which favors parallel double bonds.

    3. Electrochemistry

      Enhanced Supercapacitor Performance of MnO2 by Atomic Doping (pages 1664–1667)

      Dr. Jianli Kang, Dr. Akihiko Hirata, Lijing Kang, Dr. Xianmin Zhang, Ying Hou, Dr. Luyang Chen, Cheng Li, Dr. Takeshi Fujita, Dr. Kazuto Akagi and Prof. Mingwei Chen

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201208993

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      Electrochemical energy storage: The performance of MnO2 as a pseudo-capacitive material was enhanced by doping electrodeposited MnO2 with physically deposited gold atoms (see picture). The resulting MnO2 electrodes showed an enhanced electronic conductivity and a remarkable stability under voltammetric cycling.

    4. Asymmetric Hydrogenation

      Cooperative Catalysis through Noncovalent Interactions (pages 1668–1672)

      Dr. Weijun Tang, Steven Johnston, Dr. Jonathan A. Iggo, Dr. Neil G. Berry, Dr. Marie Phelan, Prof. Luyun Lian, Dr. John Bacsa and Prof. Jianliang Xiao

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201208774

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      One of four: A chiral phosphoric acid enables asymmetric hydrogenation of imines with an achiral iridium catalyst by virtue of noncovalent interactions. These interactions lead to the formation of a highly organized ternary complex, and the hydride is transferred highly enantioselectively.

    5. Zeolite Structures

      Criteria for Zeolite Frameworks Realizable for Target Synthesis (pages 1673–1677)

      Dr. Yi Li, Prof. Jihong Yu and Prof. Ruren Xu

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201206340

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      The huge pool of hypothetical zeolites can be screened for likely candidates for successful targeted synthesis on the basis of a set of reliable criteria derived from the observation that the local interatomic distances in all existing zeolites strictly obey several rules. For example, the average T[BOND]T and T[BOND]O distances (<DTT> and <DTO>; T is Si, Al, P, or another element) in existing zeolites (graph region highlighted in cyan) have a linear relationship.

    6. Polymer Nanoparticles

      Nanoparticles with In Vivo Anticancer Activity from Polymer Prodrug Amphiphiles Prepared by Living Radical Polymerization (pages 1678–1682)

      Dr. Simon Harrisson, Dr. Julien Nicolas, Dr. Andrei Maksimenko, Duc Trung Bui, Julie Mougin and Prof. Patrick Couvreur

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201207297

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      Magic rubber bullets: Novel anticancer nanoparticles made of well-defined polymer–drug conjugate amphiphiles are prepared by the controlled growth of a hydrophobic polyisoprene chain from a drug macroinitiator by using nitroxide-mediated polymerization (NMP; see picture). The resulting conjugates self-assembled into nanoparticles exhibiting high drug payloads and significant anticancer activities both in vitro and in vivo.

    7. Drug-Delivery Systems

      Self-Assembly of Thermally Responsive Nanoparticles of a Genetically Encoded Peptide Polymer by Drug Conjugation (pages 1683–1687)

      Jonathan R. McDaniel, Dr. Jayanta Bhattacharyya, Kevin B. Vargo, Wafa Hassouneh, Prof. Daniel A. Hammer and Prof. Ashutosh Chilkoti

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201200899

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      Nanoparticles on demand: Upon the site-specific covalent attachment of hydrophobic molecules to one end of the biopolymer backbone, chimeric polypeptides (derived from elastin-like polypeptides) can self-assemble to form thermoresponsive nanoparticles suitable for drug delivery. Molecules with a distribution coefficient greater than 1.5 imparted sufficient amphiphilicity to drive self-assembly into sub-100 nm nanoparticles (see picture).

    8. Fluorescence Imaging

      A Ratiometric Fluorescent Probe for Rapid Detection of Hydrogen Sulfide in Mitochondria (pages 1688–1691)

      Yuncong Chen, Chengcheng Zhu, Zhenghao Yang, Junjie Chen, Yafeng He, Yang Jiao, Prof. Weijiang He, Lin Qiu, Jiajie Cen and Prof. Zijian Guo

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201207701

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      Quick: An exogenously induced quick increase of the H2S concentration (80 s) in MCF-7 cells can be visualized by ratiometric imaging using a new probe (CouMC) that can target mitochondria. CouMC was constructed by combining merocyanine and coumarin fluorophores. The selective nucleophilic addition of HS to the merocyanine derivative at neutral pH is crucial for the rapid H2S detection.

    9. CO2 Adsorption

      Mechanism of Carbon Dioxide Adsorption in a Highly Selective Coordination Network Supported by Direct Structural Evidence (pages 1692–1695)

      Anna M. Plonka, Dr. Debasis Banerjee, William R. Woerner, Zhijuan Zhang, Nour Nijem, Prof. Dr. Yves J. Chabal, Prof. Dr. Jing Li and Prof. Dr. John B. Parise

      Article first published online: 11 DEC 2012 | DOI: 10.1002/anie.201207808

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      Trapped in a porous material: The position of adsorbed CO2 in a nanoporous coordination framework was determined using a combination of techniques including single-crystal X-ray diffraction, in situ X-ray powder diffraction coupled with differential scanning calorimetry, and theoretical calculations. The study reveals that the adsorbed CO2 stays in a “pocket” between two phenyl rings, interacting with the aromatic electron density (see picture).

    10. Alkali Metals

      Potassium–Alkane Interactions within a Rigid Hydrophobic Pocket (pages 1696–1699)

      Nicholas R. Andreychuk and Prof. David J. H. Emslie

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201207962

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      A NON-issue: Potassium complexes of an extremely rigid and sterically encumbered NON-donor ligand have been prepared, and the solid-state structures (see figure) feature remarkably short potassium–alkane distances. DFT calculations highlight the presence of an electrostatic cation-induced dipole potassium–alkane interaction supported by interactions between the alkane and the surrounding ligand framework.

    11. Bioorganic Chemistry

      Substrate Selectivity Analyses of Factor Inhibiting Hypoxia-Inducible Factor (pages 1700–1704)

      Dr. Ming Yang, Dr. Adam P. Hardy, Dr. Rasheduzzaman Chowdhury, Nikita D. Loik, John S. Scotti, Dr. James S. O. McCullagh, Dr. Timothy D. W. Claridge, Dr. Michael A. McDonough, Dr. Wei Ge and Prof. Dr. Christopher J. Schofield

      Article first published online: 7 JAN 2013 | DOI: 10.1002/anie.201208046

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      Substrate specificity: Biochemical and crystallographic analyses reveal the hypoxia-inducible factor hydroxylase (FIH) as being promiscuous with respect to the residues that it can hydroxylate in β-position, which in addition to Asn, Asp, and His include Leu and Ser residues. The Ser substrate is oxidized to an epimeric β-geminal diol product (see picture).

    12. Saturated Heterocycles

      SnAP Reagents for the Transformation of Aldehydes into Substituted Thiomorpholines—An Alternative to Cross-Coupling with Saturated Heterocycles (pages 1705–1708)

      Cam-Van T. Vo, Gediminas Mikutis and Prof. Dr. Jeffrey W. Bode

      Article first published online: 23 DEC 2012 | DOI: 10.1002/anie.201208064

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      It's a SnAP! The transformation of aldehydes into N-unsubstituted 3-thiomorpholines provides a convenient alternative to metal-catalyzed cross-coupling reactions, which are generally unsuited to the functionalization of saturated N-heterocycles. A copper-mediated radical cyclization is the key to the mild conditions, high functional group tolerance, and broad substrate scope offered by these reagents.

    13. Supramolecular Chemistry

      Dynamically Deformable Cube-like Hydrogen-Bonding Networks in Water-Responsive Diamondoid Porous Organic Salts (pages 1709–1712)

      Atsushi Yamamoto, Tomoya Hamada, Dr. Ichiro Hisaki, Prof. Dr. Mikiji Miyata and Dr. Norimitsu Tohnai

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201208153

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      Just add water: A cube-like hydrogen-bonding network in a fluorescent supramolecular cluster dynamically deforms upon the specific addition of a water molecule. The deformation is amplified through the conformational change of the cluster to result in the transformation of host frameworks. This transformation provides water-responsive guest-exclusion and fluorescent-modulation behaviors.

    14. Geodesic Polyarenes

      The Fold-In Approach to Bowl-Shaped Aromatic Compounds: Synthesis of Chrysaoroles (pages 1713–1717)

      Damian Myśliwiec and Dr. Marcin Stępień

      Article first published online: 17 DEC 2012 | DOI: 10.1002/anie.201208547

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      Molecular jellyfish: A new family of bowl-shaped aromatic compounds swims into view (see picture). Quite unlike true jellyfish, chrysaoroles possess a rigid skeleton, which is assembled from fused carbazole units. Their synthesis involves a fold-in step to convert a macrocyclic precursor into the bowl-shaped target molecule.

    15. Combinatorial Biosynthesis

      Combinatorial Domain Swaps Provide Insights into the Rules of Fungal Polyketide Synthase Programming and the Rational Synthesis of Non-Native Aromatic Products (pages 1718–1721)

      Dr. Anna L. Vagstad, Adam G. Newman, Philip A. Storm, Katherine Belecki, Prof. Jason M. Crawford and Prof. Craig A. Townsend

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201208550

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      Playing by the rules: Combinatorial domain swaps among “deconstructed” non-reducing polyketide synthases (NR-PKSs) revealed the rules behind product assembly (see scheme). The control exerted by individual catalytic domains was found to be sufficiently great that heterocombinations of domains from different NR-PKSs synthesized products in a predictable manner.

    16. Natural Products

      Total Syntheses of Complanadines A and B (pages 1722–1725)

      Le Zhao, Dr. Chihiro Tsukano, Dr. Eunsang Kwon, Prof. Dr. Yoshiji Takemoto and Prof. Dr. Masahiro Hirama

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201208297

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      Twice as nice: Total syntheses of dimeric alkaloids, (−)-complanadines A (1) and B (2), were achieved from (−)-lycodine. The unsymmetrical motif was assembled through direct arylation of the pyridine N-oxide. The absolute configuration and specific rotations of complanadines A and B were identified. Cbz=Benzyloxycarbonyl.

    17. Synthetic Studies on Pseudo-Dimeric Lycopodium Alkaloids: Total Synthesis of Complanadine B (pages 1726–1730)

      James N. Newton, Dr. Daniel F. Fischer and Prof. Richmond Sarpong

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201208571

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      Two approaches to the total synthesis of the dimeric Lycopodium alkaloid complanadine B have been achieved. In the first approach (see scheme; route 1), a keto lycodine unit is coupled to another lycodine unit whereas in the latter approach (route 2), selective oxygenation of one of two pseudo-benzylic positions is achieved.

    18. Asymmetric Catalysis

      Kinetic Resolution of Tertiary Alcohols: Highly Enantioselective Access to 3-Hydroxy-3-Substituted Oxindoles (pages 1731–1734)

      Dr. Shenci Lu, Si Bei Poh, Woon-Yew Siau and Prof. Yu Zhao

      Article first published online: 7 JAN 2013 | DOI: 10.1002/anie.201209043

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      Enantioselective: The first highly enantioselective kinetic resolution of 3-hydroxy-3-substituted oxindoles has been developed through oxidative esterification catalyzed by a N-heterocyclic carbene (see picture). This method uses a simple procedure and provides 3-hydroxy-oxindoles with various substituents at the 3-position in excellent enantiopurity. S=selectivity.

    19. Conjugated Polymers

      Nanostructure Engineering and Doping of Conjugated Carbon Nitride Semiconductors for Hydrogen Photosynthesis (pages 1735–1738)

      Zhenzhen Lin and Prof. Xinchen Wang

      Article first published online: 7 JAN 2013 | DOI: 10.1002/anie.201209017

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      Going flat out: Simultaneous modifications of the textural, surface, and electronic structures of a rigid conjugated carbon nitride polymer has been achieved using direct co-condensation of urea and Ph4BNa. This method gives boron-doped carbon nitride nanosheets (see picture) that optimize the capture of light, improve the charge-separation kinetics, and enhance the surface reactivity for hydrogen photosynthesis.

    20. C[BOND]H Amination

      Enantio- and Regioselective Intermolecular Benzylic and Allylic C[BOND]H Bond Amination (pages 1739–1742)

      Yota Nishioka, Dr. Tatsuya Uchida and Prof. Tsutomu Katsuki

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201208906

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      Smooth salen: Ru(CO)–salen complex 1 is an effective catalyst for asymmetric benzylic and allylic C[BOND]H bond amination using 2-(trimethylsilyl)ethanesulfonyl azide (SESN3) as the nitrene source. The reaction proceeded with high enantioselectivity and excellent regioselectivity. An ethyl group can be selectively aminated, even in the presence of an n-propyl group. No migration or isomerization of the double bond was observed.

    21. Asymmetric Catalysis

      Asymmetric Intramolecular Oxa-Michael Reactions of Cyclohexadienones Catalyzed by a Primary Amine Salt (pages 1743–1747)

      Wenbin Wu, Xin Li, Huicai Huang, Xiaoqian Yuan, Junzhu Lu, Kailong Zhu and Prof. Dr. Jinxing Ye

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201206977

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      Michael brings the rings: An asymmetric intramolecular oxa-Michael reaction involving iminium activation has been developed. This reaction provides enantioenriched 1,4-dioxane derivatives with up to 99 % yield and 98 % ee. The method allows for concise and stereoselective access to stereodiverse, complex tetracyclic compounds containing a bicyclo[2.2.2]octan-2-one backbone with multiple chiral centers.

    22. Synthetic Methods

      Synthesis and Properties of Perfluoroalkyl Phosphine Ligands: Photoinduced Reaction of Diphosphines with Perfluoroalkyl Iodides (pages 1748–1752)

      Dr. Shin-ichi Kawaguchi, Yoshiaki Minamida, Takashi Ohe, Dr. Akihiro Nomoto, Dr. Motohiro Sonoda and Prof. Dr. Akiya Ogawa

      Article first published online: 4 JAN 2013 | DOI: 10.1002/anie.201207383

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      A ‘F'lurry of activity: The title reaction provides a convenient procedure for direct synthesis of perfluoroalkylated phosphines. The synthesized phosphine n-C10F21PPh2 forms a complex with palladium(II) to give 1 and several runs of coupling reactions are attained with n-C10F21PPh2 by using a fluorous/organic biphasic system.

    23. Indole Synthesis

      A Variation of the Fischer Indolization Involving Condensation of Quinone Monoketals and Aliphatic Hydrazines (pages 1753–1757)

      Dr. Jinzhu Zhang, Zhiwei Yin, Patrick Leonard, Jing Wu, Kate Sioson, Che Liu, Robert Lapo and Prof. Dr. Shengping Zheng

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201207533

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      A new twist: A one-pot nitrous acid free, diazonium-free, and transition-metal-free variation of the Fischer indole synthesis has been developed. Condensation of quinone monoketals and aliphatic hydrazine hydrochlorides afforded indoles via intermediate alkylaryldiazenes. This method will complement the classical Fischer indole synthesis by providing indoles in two steps from widely available phenols under mild conditions.

    24. Synthetic Methods

      Ruthenium-Triggered Ring Opening of Ethynylcyclopropanes: [3+2] Cycloaddition with Aldehydes and Aldimines Involving Metal Allenylidene Intermediates (pages 1758–1762)

      Dr. Yoshihiro Miyake, Satoshi Endo, Dr. Taichi Moriyama, Prof. Dr. Ken Sakata and Prof. Dr. Yoshiaki Nishibayashi

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201207801

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      It's complex: Ruthenium-catalyzed [3+2] cycloaddition of ethynylcyclopropanes with aldehydes and aldimines has been found to give the corresponding 2-ethynyltetrahydrofurans or -pyrrolidines in high to excellent yields. In both cases, the formation of a ruthenium allenylidene complex as a key reactive intermediate is supported by density functional theory calculations. Cp*=η5-C5Me5.

    25. Antiaromaticity

      Antiaromatic Supramolecules: F⋅⋅⋅S, F⋅⋅⋅Se, and F⋅⋅⋅π Intermolecular Interactions in 32 π Expanded Isophlorins (pages 1763–1767)

      Tullimilli Y. Gopalakrishna, Dr. J. Sreedhar Reddy and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 23 DEC 2012 | DOI: 10.1002/anie.201207987

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      Count against: Stable and planar antiaromatic, expanded vinylogous isophlorins encourage chalcogen–fluorine noncovalent interactions. The wide cavity of the macrocycle accommodates covalently bound fluorine substituents, thus leading to multiple nonbonding interactions

    26. Benzazepine Synthesis

      Palladium-Catalyzed Oxidative Cycloaddition through C[BOND]H/N[BOND]H Activation: Access to Benzazepines (pages 1768–1772)

      Lei Wang, Jiayao Huang, Shiyong Peng, Dr. Hui Liu, Prof. Dr. Xuefeng Jiang and Prof. Dr. Jian Wang

      Article first published online: 23 DEC 2012 | DOI: 10.1002/anie.201208076

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      Rings beget rings: Benzazepines, well-known structural design elements in medicinal chemistry, are readily prepared by a one-pot palladium-catalyzed oxidative cycloaddition of isatins with various alkynes.

    27. Photoexcited Hydride Cluster

      Bimetallic Activation of 2-Alkanones through Photo-Induced α-Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex (pages 1773–1776)

      Prof. Dr. Hiroharu Suzuki, Ryuichi Shimogawa, Yuki Muroi, Dr. Toshiro Takao, Prof. Dr. Masato Oshima and Dr. Gen-ichi Konishi

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201208185

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      Hydrogen abstraction in the spotlight: UV irradiation (365 nm) of dinuclear ruthenium tetrahydride, [(Cp*Ru)(μ-H)4(RuCp*)] (Cp*=η5-C5Me5), in a 2-alkanone, such as acetone or 2-butanone, resulted in the formation of dinuclear oxatrimethylenemethane complexes, [(Cp*Ru)(μ-η31-CH2COCHR)(μ-H)2(RuCp*)] (R=H and CH3), through hydrogen abstraction from the α and α′ positions of the carbonyl group.

    28. Asymmetric Arylation

      Hydroxorhodium/Chiral Diene Complexes as Effective Catalysts for the Asymmetric Arylation of 3-Aryl-3-hydroxyisoindolin-1-ones (pages 1777–1780)

      Dr. Takahiro Nishimura, Akira Noishiki, Yusuke Ebe and Prof. Dr. Tamio Hayashi

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201208593

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      Water is out, aryl is in! Asymmetric synthesis of isoindoline-1-ones bearing an α-triaryl-substituted stereogenic center was realized in the enantioselective addition of arylboroxines to 3-aryl-3-hydroxyisoindolin-1-ones in the presence of a hydroxorhodium/chiral diene catalyst, where cyclic N-carbonyl ketimines were generated in situ by dehydration.

    29. Oxidative Coupling

      Redox-Controlled Selectivity of C[BOND]H Activation in the Oxidative Cross-Coupling of Arenes (pages 1781–1784)

      Dr. Xacobe C. Cambeiro, Tanya C. Boorman, Dr. Pengfei Lu and Dr. Igor Larrosa

      Article first published online: 23 DEC 2012 | DOI: 10.1002/anie.201209007

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      Gold brings us together: Taking advantage of the orthogonal reactivities of AuI and AuIII towards C[BOND]H activation of electron-poor and electron-rich arenes, respectively, a novel approach for the synthesis of biaryls through double C[BOND]H activation is proposed. Stoichiometric studies demonstrate that these oxidative couplings occur with high selectivity at low temperature.

    30. Enantioselective Silylation

      Copper-Catalyzed Addition of Nucleophilic Silicon to Aldehydes (pages 1785–1788)

      Virginie Cirriez, Corentin Rasson, Thomas Hermant, Dr. Julien Petrignet, Dr. Jesús Díaz Álvarez, Dr. Koen Robeyns and Prof. Olivier Riant

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201209020

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      How to train your silane: A new family of chiral copper(I) complexes that bear a bifluoride counteranion were prepared and used in the first example of the enantioselective transfer of a silyl group to an aldehyde. This procedure provides fast access to non-racemic α-hydroxysilanes in high enantioselectivities.

    31. Water Oxidation

      Chemical and Visible-Light-Driven Water Oxidation by Iron Complexes at pH 7–9: Evidence for Dual-Active Intermediates in Iron-Catalyzed Water Oxidation (pages 1789–1791)

      Dr. Gui Chen, Lingjing Chen, Dr. Siu-Mui Ng, Dr. Wai-Lun Man and Prof. Tai-Chu Lau

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201209116

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      Ironing out a solution: Chemical and visible-light-driven water oxidation by iron complexes and iron salts at pH 7–9 has been investigated. The iron complexes and salts act as precatalysts (see scheme) to produce α-Fe2O3 nanoparticles that are the real catalyst for the water oxidation with a turnover number over 1000.

    32. Heterogeneous Catalysis

      Macro- and Mesoporous Polymers Synthesized by a CO2-in-Ionic Liquid Emulsion-Templating Route (pages 1792–1795)

      Li Peng, Prof. Jianling Zhang, Jianshen Li, Prof. Buxing Han, Zhimin Xue and Guanying Yang

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201209255

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      Poring over polymers: Highly porous polymers with hierarchical macro- and mesoporous structures were synthesized by using the title method and UV radiation. The porosity properties of the polymers can be easily tuned by controlling the CO2 pressure used, and the polymers have potential applications in catalysis. IL=ionic liquid, PAM=polyacrylamide.

    33. Helicenes

      Modular Synthesis, Orthogonal Post-Functionalization, Absorption, and Chiroptical Properties of Cationic [6]Helicenes (pages 1796–1800)

      Franck Torricelli, Dr. Johann Bosson, Dr. Céline Besnard, Mahshid Chekini, Prof. Thomas Bürgi and Prof. Jérôme Lacour

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201208926

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      Pick and choose: Novel cationic diaza-, azaoxo-, and dioxo[6]helicenes are readily prepared and functionalized selectively by orthogonal aromatic electrophilic and vicarious nucleophilic substitutions (see scheme). Reductions, cross-coupling, or condensation reactions introduce additional diversity and allow tuning of the absorption properties up to the near-infrared region. The diaza salts can be resolved into single enantiomers.

    34. Biradicals

      Conversion of a Singlet Silylene to a stable Biradical (pages 1801–1805)

      Dr. Kartik Chandra Mondal, Prof. Dr. Herbert W. Roesky, Martin C. Schwarzer, Prof. Dr. Gernot Frenking, Dr. Igor Tkach, Hilke Wolf, Daniel Kratzert, Dr. Regine Herbst-Irmer, Benedikt Niepötter and Prof. Dr. Dietmar Stalke

      Article first published online: 20 DEC 2012 | DOI: 10.1002/anie.201204487

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      Silicon becomes colored: Stable biradicals were prepared from an N-heterocyclic carbene stabilized SiCl2 and a cyclic alkyl(amino)carbene, and characterized as two polymorphs. The deep-blue crystals of one polymorph are stable upon exposure to air for about a week, while the solution in THF decomposes rapidly when exposed to air. In a side reaction, the different carbene species react with each other under C[BOND]H activation and C[BOND]C bond formation in the presence of the biradical.

    35. Hydroaminoalkylation

      Aminopyridinato Titanium Catalysts for the Hydroaminoalkylation of Alkenes and Styrenes (pages 1806–1809)

      Jaika Dörfler and Prof. Sven Doye

      Article first published online: 12 DEC 2012 | DOI: 10.1002/anie.201206027

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      The linear product is formed as the major product when in situ generated titanium complexes with aminopyridinato ligands are used as catalysts for hydroaminoalkylation reactions of styrenes (see scheme). The reaction is not limited to the use of N-methylanilines and for the first time can be performed with N-alkylanilines bearing alkyl groups larger than methyl, or even with dialkylamines. The best selectivities in favor of a linear product are better than 90:10.

    36. Terpene Biosynthesis

      Rapid Chemical Characterization of Bacterial Terpene Synthases (pages 1810–1812)

      Patrick Rabe and Dr. Jeroen S. Dickschat

      Article first published online: 10 JAN 2013 | DOI: 10.1002/anie.201209103

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      Modern sequencing techniques deliver more and more genetic information about bacterial terpene cyclases. Chemical characterization of these enzymes must stay up to date with these developments. For this purpose a rapid and efficient method for the characterization of bacterial terpene cyclases by heterologous expression in E. coli and direct headspace analysis was developed. The products of six bacterial terpene cyclases have been identified (see structures).

    37. Molecular Dynamics Simulations

      An Ab Initio Microscope: Molecular Contributions to the Femtosecond Time-Dependent Fluorescence Shift of a Reichardt-Type Dye (pages 1813–1816)

      Christoph Allolio, Dr. Mohsen Sajadi, Prof. Dr. Nikolaus P. Ernsting and Prof. Dr. Daniel Sebastiani

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201204532

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      Beyond bulk dielectric relaxation: The experimentally observed time-dependent Stokes shift of a molecular probe (MQ) can be explained by molecular dynamics simulations in combination with DFT calculations. Decomposition of the MD trajectories shows that an important contribution to the time-dependent Stokes shift originates from a group of water molecules that strongly interact with the molecular dipole of MQ.

    38. Cumulenes

      Synthesis and Structure of Tetraarylcumulenes: Characterization of Bond-Length Alternation versus Molecule Length (pages 1817–1821)

      Johanna A. Januszewski, Dominik Wendinger, Christian D. Methfessel, Dr. Frank Hampel and Prof. Rik R. Tykwinski

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201208058

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      BLA=0? Not so fast! A series of tetraarylcumulenes up to the length of a [9]cumulene has been synthesized and analyzed by X-ray crystallography. The structural data show a distinct reduction in bond-length alternation (BLA) as a function of molecule length, but this trend appears to reach a limit before a cumulenic structure with BLA=0 is achieved.

    39. Protein–Ligand Complexes

      Dissecting the Hydrophobic Effect on the Molecular Level: The Role of Water, Enthalpy, and Entropy in Ligand Binding to Thermolysin (pages 1822–1828)

      Dr. Adam Biela, Nader N. Nasief, Michael Betz, Dr. Andreas Heine, Prof. Dr. David Hangauer and Prof. Dr. Gerhard Klebe

      Article first published online: 2 JAN 2013 | DOI: 10.1002/anie.201208561

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      The hydrophobic effect is associated with the successive replacement of water molecules in the binding site of a protein by hydrophobic groups of the ligand. Although the hydrophobic effect is assumed to be entropy-driven, large changes in enthalpy and entropy are observed with the model system thermolysin. Structural changes in the binding features of the water molecules ultimately determine the thermodynamics of the hydrophobic effect.

    40. Hybrid Vesicles

      Controlling Molecular Recognition with Lipid/Polymer Domains in Vesicle Membranes (pages 1829–1833)

      Matthias Schulz, Stefan Werner, Jun.-Prof. Dr. Kirsten Bacia and Prof. Dr. Wolfgang H. Binder

      Article first published online: 23 DEC 2012 | DOI: 10.1002/anie.201204959

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      The molecular recognition between cholera toxin B and GM1-functionalized phospholipid/block copolymer hybrid membranes can be controlled by varying the lipid/block copolymer composition. Confocal laser scanning microscopy and fluorescence correlation spectroscopy were used to study the protein–receptor interaction and dynamic processes in the membrane.

    41. Main-Group Chemistry

      [Ge12{FeCp(CO)2}8{FeCp(CO)}2]: A Ge12 Core Resembles the Arrangement of the High-Pressure Modification Germanium (II) (pages 1834–1838)

      Dr. Christian Schenk, Dr. Florian Henke and Prof. Dr. Andreas Schnepf

      Article first published online: 3 JAN 2013 | DOI: 10.1002/anie.201207224

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      Similar yet different: The reaction of a GeBr solution with K[FeCp(CO)2] (Cp=η-C5H5) gives [Ge12{FeCp(CO)2}8{FeCp(CO)}2] (1), whose oblong, highly cross-linked cluster core reveals a cut-out of the high-pressure solid-state structure of germanium (II) (see scheme). Mass spectrometric investigations on the gas-phase species [Ge6{FeCp(CO)2}6{FeCp(CO)}] (2) and theoretical calculations on 1 and 2 illuminate the formation of the metalloid cluster 1.

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